JP2009540562A - Electronic package and manufacturing method thereof - Google Patents

Abstract

  An electronic package comprising an interfacial coating comprising a cured product of a silicone resin between a first inorganic barrier coating and a second inorganic barrier coating, and a method of manufacturing the electronic package.

Description

  The present invention relates to an electronic package, and more particularly to an electronic package that includes an interfacial coating between a first inorganic barrier coating and a second inorganic barrier coating. This interfacial coating includes a cured product of a silicone resin. The present invention relates to a method for manufacturing the electronic package.

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of US Provisional Patent Application No. 60/81223, filed June 5, 2006, based on Section 119 (e) of the US Patent Act. US Provisional Patent Application No. 60/81223 is hereby incorporated by reference.

  Barrier coatings play an important role in a wide range of applications including electronic packaging, food packaging and surface treatment by protecting sensitive materials from air, moisture and environmental pollutants. In particular, barrier coatings are frequently applied to electronic devices to protect sensitive electrical contacts from various gases and liquids in the environment. As a result, such coatings increase the reliability and useful life of many consumer products.

  Barrier coatings consisting of a single layer of an inorganic material such as a metal oxide or metal nitride are known in the art. However, such coatings are often brittle for use on materials with high thermal expansion, such as polymer substrates. Stress is generated in the barrier layer due to the difference in coefficient of thermal expansion between the substrate and the coating. Thermally induced stresses can cause cracking of the barrier coating, thereby reducing coating effectiveness and device reliability.

  One approach to reduce crack formation in the barrier coating is to deposit an organic coating adjacent to the barrier coating. These multilayer coatings typically include alternating layers of inorganic material and polymer material. For example, WO 03/016589 A1 by Czeremuszkin et al. Discloses a multilayer structure comprising an organic substrate layer and a multilayer penetration barrier on the substrate, which a) contacts the surface of the substrate layer. A first inorganic coating; and b) a first organic coating in contact with the surface of the inorganic coating.

  WO 02 / 091064A2 by Ziegler et al. Discloses a method of manufacturing a flexible barrier material that prevents the passage of water and oxygen to devices incorporating organic display materials. The method includes the steps of preparing a polymer layer, depositing an inorganic barrier layer on the polymer layer by ion-assisted sputtering or vapor deposition, and depositing a second polymer layer on the inorganic barrier layer. Including, thereby providing a composite barrier material that can be associated with an electronic display device that prevents degradation of properties as a result of the passage of water and / or oxygen.

  US Patent Application Publication No. 2003 / 0203210A1 by Graff et al. Discloses a multilayer barrier coating on a flexible substrate comprising alternating polymer and inorganic layers. Here, both the layer directly adjacent to the flexible substrate and the uppermost separation layer may be inorganic layers.

  EP 1 139 453 A2 discloses, among other things, a self-luminous device comprising an EL element, a film made of an inorganic material covering the EL element, and a film made of an organic material covering the film made of the inorganic material Is disclosed.

  US Pat. No. 5,952,778 to Haskal et al. Provides an improved protective cover comprising a first layer of passivating metal, a second layer of inorganic dielectric material, and a third layer of polymer. An encapsulated organic light emitting device is disclosed.

  US Pat. No. 6,570,352 B2 by Graff et al. Discloses an encapsulated organic light emitting device comprising a substrate, an organic light emitting layer stack adjacent to the substrate, and at least one first barrier stack adjacent to the organic light emitting device. A device is disclosed, the at least one first barrier stack including at least one first barrier layer and at least one first decoupling layer, wherein the at least one first barrier stack is organic. A light emitting device is enclosed.

International Publication No. 03/016589 A1 International Publication No. 02 / 091064A2 US Patent Application Publication No. 2003 / 0203210A1 European Patent Application Publication No. 1139453A2 US Pat. No. 5,952,778 US Pat. No. 6,570,352 B2

  Although the above cited references disclose coatings with a wide range of barrier properties, there continues to be a need for coatings with excellent resistance to environmental factors, particularly water vapor and oxygen.

The present invention
A substrate,
At least one electronic device disposed on or in the substrate and having electrical contacts;
A first inorganic barrier coating on the substrate and electronic device;
A first interface coating on a first inorganic barrier coating in an upper region of the electronic device, the first interface coating comprising a cured product of a silicone resin;
A second inorganic barrier coating on the first interface coating and on any portion of the first inorganic barrier coating not covered by the first interface coating, wherein at least a portion of each electrical contact has a coating. Does not relate to electronic packages.

The present invention also relates to a method of manufacturing an electronic package, the method comprising:
Forming a first inorganic barrier coating on the substrate and on at least one electronic device disposed on or in the substrate and having electrical contacts;
Forming a first interfacial coating comprising a cured product of a silicone resin on the first inorganic barrier coating in the upper region of the electronic device; and being coated on and by the first interfacial coating Forming a second inorganic barrier coating on any portion of the non-first inorganic barrier coating, wherein no coating is formed on at least a portion of each electrical contact.

The electronic package of the present invention is typically lighter, thinner and more durable than conventional electronic packages. Moreover, the complex of the inorganic barrier and interfacial coatings of the electronic package, low water vapor transmission rate, typically have a ^{1 × 10 -7 g / m 2} / day to 3 g / m ² / day. The coating also has low permeability to oxygen and metal ions such as copper and aluminum. Furthermore, the coating can be transparent or non-transparent to light in the visible region of the electromagnetic spectrum. Furthermore, this coating has high resistance to cracking and low compressive stress.

  The method of manufacturing the electronic package of the present invention can be carried out using conventional equipment and techniques and readily available silicone compositions. For example, the inorganic barrier coating can be deposited using chemical vapor deposition and physical vapor deposition. Moreover, the interfacial coating can be formed using conventional methods of applying and curing the silicone composition. In addition, the method of the present invention can be extended to a high-throughput manufacturing method.

  The electronic package of the present invention is useful for manufacturing a wide range of consumer electronic products including light-emitting arrays or displays, calculators, telephones, televisions, and mainframe and personal computers.

1 is a cross-sectional view of an embodiment of an electronic package according to the present invention. A second interfacial coating on the second inorganic barrier coating at least in the upper region of the electronic device, the second interfacial coating comprising a cured product of a silicone resin, and the second interfacial coating and the second interfacial coating FIG. 6 is a cross-sectional view of the above embodiment of an electronic package further comprising a third inorganic barrier coating on any portion of the second inorganic barrier coating not covered by the coating.

  As shown in FIG. 1, an embodiment of an electronic package according to the present invention includes a substrate 100 and at least one electronic device 110 disposed on or in the substrate 100 and having electrical contacts (not shown); A first inorganic barrier coating 120 on the substrate 100 and on the electronic device 110, and a first interfacial coating on the first inorganic barrier coating 120 in the upper region of the electronic device 110, wherein the cured product of the silicone resin is A first interfacial coating 130 comprising, and a second inorganic barrier coating 140 on the first interfacial coating 130 and on any portion of the first inorganic barrier coating 120 not covered by the first interfacial coating 130. And at least a portion of each electrical contact has no coating.

  The substrate may be any rigid or flexible material having a planar outline, a complex outline or an irregular outline. The substrate may be transmissive or non-transmissive to light in the visible region of the electromagnetic spectrum (about 400 nm to about 700 nm). Also, the substrate can be a conductor, a semiconductor, or a nonconductor.

  Examples of the substrate include semiconductors such as silicon having a surface layer of silicon, silicon dioxide, silicon carbide, indium phosphide, and gallium arsenide; quartz; quartz glass; aluminum oxide; ceramics; glass; metal foil; polyethylene, polypropylene, polystyrene, Polyolefins such as polyethylene terephthalate (PET) and polyethylene naphthalate; Fluorocarbon polymers such as polytetrafluoroethylene and polyvinyl fluoride; Polyamide such as nylon; Polyimide; Polyester such as poly (methyl methacrylate); Epoxy resin; Polyether; Polysulfone; as well as polyethersulfone, but are not limited to these.

  The electronic package includes at least one electronic device. The electronic device may be a separate device or an integrated circuit. Electronic devices have electrical contacts that transmit and receive electrical signals. In the case of integrated circuits, electrical contacts or bond pads (ie, I / O terminals) are typically placed on the periphery of the device. The number of bond pads per integrated circuit can range from about 4 to about 2,000, depending on the complexity of the circuit. The bond pad is made of a conductive metal, typically aluminum, copper or alloys thereof.

  The electronic device can be placed on or in the substrate. For example, bipolar transistors are typically located in the substrate, whereas thin film transistors such as field effect transistors (FETs) are typically located on the surface of the substrate.

  Examples of separate devices include PIN diodes, voltage reference diodes, varactor diodes, avalanche diodes, DIACs, Gunn diodes, snap diodes, IMPATT diodes, tunnel diodes, Zener diodes, normal (pn) diodes, Schottky diodes, etc. Diodes; bipolar transistors including insulated gate bipolar transistors (IGBTs) and Darlington transistors; metal oxide semiconductor FETs (MOSFETs); junction FETs (JFETs); metal-semiconductor FETs (MESFETs); organic FETs; Transistors such as field effect transistors (FETs) including degree transistors (HEMT) and thin film transistors (TFTs) (including organic field effect transistors) Thyristors such as DIAC, TRIAC, silicon controlled rectifier (SCR), distributed buffer-gate turn-off (DB-GTO) thyristor, gate turn-off (GTO) thyristor, MOFSET controlled thyristor (MCT), improved anode-gate turn-off (MA-) GTO) thyristors, electrostatic induction thyristors (SITh), and electric field controlled thyristors (FCTh); varistors; resistors; capacitors; capacitors; thermistors; and photodiodes, solar cells (eg, CIGS solar cells and organic photovoltaic cells), phototransistors , Photomultiplier tubes, optical integrated circuit (IOC) devices, light dependent resistors, laser diodes, light emitting diodes (LEDs), and small molecule OLEDs (SM-OLEDs) and polymer light emitting diodes (PLEDs) Optoelectronic devices such as organic light emitting diode (OLED) including but not limited to.

  Examples of integrated circuits include monolithic integrated circuits such as RAM (random access memory) (including DRAM and SRAM) and memory ICs including ROM (read only memory); logic circuits; analog integrated circuits; thin film hybrid ICs and thick films Examples include, but are not limited to, hybrid integrated circuits including hybrid ICs; thin film batteries; solar cells and fuel cells.

  The first inorganic barrier coating may be any barrier coating comprising an inorganic material that has low permeability to water vapor (humidity). The inorganic material can be a conductor, a nonconductor, or a semiconductor.

  The first inorganic barrier coating may be a single layer coating consisting of one layer of inorganic material, or the directly adjacent layers comprise different inorganic materials (ie, the inorganic materials have different compositions and / or properties) It may be a multilayer coating consisting of two or more layers of at least two different inorganic materials. If the layer of inorganic material in the single layer coating contains more than one element (eg TiN), this layer can be a gradient layer where the composition of the layer varies with thickness. Similarly, if at least one layer of inorganic material in the multilayer coating contains more than one element, this layer can be a gradient layer. Multi-layer coatings typically include 2 to 7 layers, alternatively 2 to 5 layers, alternatively 2 to 3 layers.

  Single layer inorganic barrier coatings typically have a thickness of 0.03 μm to 3 μm, alternatively 0.1 μm to 1 μm, alternatively 0.2 μm to 0.8 μm. The multilayer inorganic barrier coating typically has a thickness of 0.06 μm to 5 μm, alternatively 0.1 μm to 3 μm, alternatively 0.2 μm to 2.5 μm. If the thickness of the inorganic barrier coating is less than 0.03 μm, the permeability of the coating to moisture may be too high for some applications. If the thickness of the inorganic barrier coating exceeds 5 μm, the inorganic barrier coating may be susceptible to cracking.

  The first inorganic barrier coating may be transmissive or non-transmissive to light in the visible region of the electromagnetic spectrum (about 400 nm to about 700 nm). The transmissive inorganic barrier coating typically has a transmittance of at least 30%, alternatively at least 60%, alternatively at least 80% for light in the visible region of the electromagnetic spectrum.

  Examples of inorganic materials include metals such as aluminum, calcium, magnesium, nickel and gold; metal alloys such as aluminum magnesium alloy, silver magnesium alloy, lithium aluminum alloy, indium magnesium alloy and aluminum calcium alloy; silicon dioxide, aluminum oxide , Titanium (II) oxide, titanium (III) oxide, barium oxide, beryllium oxide, magnesium oxide, tin (II) oxide, tin (IV) oxide, indium (III) oxide, lead (II) oxide, lead oxide (IV) ), Zinc oxide, tantalum oxide (V), yttrium oxide (III), diphosphorus pentoxide, boron oxide, zirconium oxide (IV), and calcium oxide; indium tin oxide (ITO), indium zinc oxide ( IZO) and indium oxide Mixed oxides such as silicon; nitrides such as silicon nitride, titanium nitride, aluminum nitride, indium (III), and gallium nitride; mixed nitrides such as silicon aluminum nitride; silicon oxynitride, aluminum oxynitride, and boron oxynitride Oxynitrides such as silicon carbide, aluminum carbide, boron carbide and calcium carbide; oxycarbides such as silicon oxycarbide; mixed oxynitrides such as silicon oxynitride silicon and titanium silicon oxynitride; magnesium fluoride and fluorine Fluorides such as calcium fluoride; and carbonitrides such as silicon carbonitride include, but are not limited to.

  The first inorganic barrier coating can be formed as described below in the method of manufacturing the electronic package of the present invention.

  A first interfacial coating is present on the first inorganic barrier coating in the upper region of the electronic device. Typically, the upper area of the electronic device is slightly larger than the size of the device. For example, the upper region of an electronic device is typically 105% to 110% larger than the device size, alternatively 110% to 120% larger.

  The first interfacial coating includes a cured product of at least one silicone resin. As used herein, the term “cured product of silicone resin” refers to a crosslinked silicone resin having a three-dimensional network structure. The first interfacial coating may be a single layer coating consisting of a single layer of a cured product of silicone resin, or may comprise a cured product in which the directly adjacent layers are different (ie, the cured product has a different composition and / or It may also be a multilayer coating consisting of two or more layers of cured products of at least two different silicone resins (or have properties). Multi-layer coatings typically include 2 to 7 layers, alternatively 2 to 5 layers, alternatively 2 to 3 layers.

  Single layer interface coatings typically have a thickness of 0.03 μm to 30 μm, alternatively 0.1 μm to 10 μm, alternatively 0.1 μm to 1.5 μm. The multi-layer interface coating typically has a thickness of 0.06 μm to 30 μm, alternatively 0.2 μm to 10 μm, alternatively 0.2 μm to 3 μm. If the thickness of the interface coating is less than 0.03 μm, the coating can be discontinuous. If the thickness of the interfacial coating exceeds 30 μm, the coating may exhibit low adhesion and / or cracks.

  The first interfacial coating typically exhibits high transparency. For example, the first interfacial coating typically has a% transmittance of at least 90%, alternatively at least 92%, alternatively at least 94% for light in the visible region of the electromagnetic spectrum (about 400 nm to about 700 nm). Have

  The silicone resin, the method of preparing the resin, and the method of preparing the first interface layer are described below in the method of manufacturing the electronic package of the present invention.

  The second inorganic barrier coating is present on the first interfacial coating and on any portion of the first inorganic barrier coating not covered by the first interfacial coating. The second inorganic barrier coating is similar to that described and illustrated above with respect to the first inorganic barrier coating of the electronic package.

  The electronic package of the present invention may further include at least one interfacial coating and at least one inorganic barrier coating alternately on the second inorganic barrier coating. For example, as shown in FIG. 2, the above embodiment of the electronic package is a second interfacial coating on the second inorganic barrier coating 140 at least in the upper region of the electronic device 110, wherein the cured product of the silicone resin. A second interfacial coating 150 comprising: a third inorganic barrier coating 160 on the second interfacial coating 150 and on any portion of the second inorganic barrier coating 140 not covered by the second interfacial coating 150; May further be included.

A method of manufacturing an electronic package according to the present invention comprises:
Forming a first inorganic barrier coating on the substrate and on at least one electronic device disposed on or in the substrate and having electrical contacts;
Forming a first interfacial coating comprising a cured product of a silicone resin on the first inorganic barrier coating in the upper region of the electronic device; and being coated on and by the first interfacial coating Forming a second inorganic barrier coating on any portion of the non-first inorganic barrier coating, wherein no coating is formed on at least a portion of each electrical contact.

  In accordance with the above-described method of manufacturing an electronic package, a first inorganic barrier coating is formed on a substrate and at least one electronic device disposed on or in the substrate and having electrical contacts. The first inorganic barrier coating, substrate, and electronic device are similar to those described and exemplified above for the electronic package.

  Methods for forming inorganic barrier coatings are known in the art. For example, inorganic barrier coatings include chemical vapor deposition methods such as thermal chemical vapor deposition, plasma enhanced chemical vapor deposition, photochemical vapor deposition, electron cyclotron resonance, inductively coupled plasma, magnetically confined plasma, and jet vapor deposition; and RF sputtering, atomic It can be deposited using layer deposition and physical vapor deposition methods such as DC magnetron sputtering.

  A first interfacial coating is formed on the first inorganic barrier coating in the upper region of the electronic device, the first interfacial coating comprising a cured product of silicone resin. The first interfacial coating is similar to that described and illustrated above for the electronic package of the present invention.

  The first interfacial coating can be formed using various methods. For example, the first interfacial coating may comprise: (i) applying a curable silicone composition comprising a silicone resin on the first inorganic barrier coating in the upper region of the electronic device to form a film; and (ii) ) It can be formed by a first method comprising curing the silicone resin of the film.

  The curable silicone composition may be any curable silicone composition comprising at least one silicone resin. Curable silicone compositions and methods for their preparation are known in the art. Examples of curable silicone compositions include, but are not limited to, hydrosilylation curable silicone compositions, condensation curable silicone compositions, radiation curable silicone compositions and peroxide curable silicone compositions.

  The silicone resin of the curable silicone composition may contain T siloxane units, T siloxane units and Q siloxane units, or T siloxane units and / or Q siloxane units in combination with M siloxane units and / or D siloxane units. For example, the silicone resin can be a T resin, TQ resin, MT resin, DT resin, MDT resin, MQ resin, DQ resin, MDQ resin, MTQ resin, DTQ resin or MDTQ resin.

  Silicone resins typically contain silicon-bonded reactive groups that can react in the presence or absence of a catalyst to form a cured product of the silicone resin. Examples of silicon-bonded reactive groups include, but are not limited to, -H, alkenyl, alkynyl, -OH, hydrolyzable groups, alkenyl ethers, acryloyloxyalkyl, substituted acryloyloxyalkyl, and epoxy-substituted organic groups. Not.

Silicone resins are typically 500 to 1,000,000, alternatively 1,000 to 100,000, alternatively 1,000 to 50,000, alternatively 1,000 to 20,000. Alternatively, it has a weight average molecular weight (M _w ) of 1,000 to 10,000. Here, the molecular weight is determined by gel permeation chromatography using a differential refractive index detector and polystyrene conversion.

  Hydrosilylation-curable silicone compositions typically include a silicone resin having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule and an amount of organosilicon compound sufficient to cure the silicone resin An organosilicon compound having on average at least two silicon-bonded alkenyl groups or silicon-bonded alkenyl groups capable of reacting with silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the silicone resin, and a catalytic amount of hydrosilyl Catalyst.

In accordance with the first embodiment, the hydrosilylation curable silicone composition comprises (A) formula (R ¹ R ² ₂ SiO _1/2 ) _w (R ² ₂ SiO _2/2 ) _x (R ² SiO _3/2 ) _y (SiO _4/2 ) _z (I) wherein each R ¹ is independently C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl (both free of aliphatic unsaturation). R ² is independently R ¹ or alkenyl, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, and z is 0 to 0.9. Wherein y + z is 0.1 to 1 and w + x + y + z = 1), with an average of at least two silicon-bonded alkenyl groups per molecule, and (B) a silicone resin An amount of at least two silicon bonds per molecule, sufficient to cure Comprising an organic silicon compound having a hydrogen atom, a hydrosilylation catalyst (C) a catalytic amount.

Component (A) has the formula (R ¹ R ² ₂ SiO _1/2 ) _w (R ² ₂ SiO _2/2 ) _x (R ² SiO _3/2 ) _y (SiO _4/2 ) _z (I) (formula In which each R ¹ is independently C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl (both free of aliphatic unsaturation), and each R ² is independently R ¹ or alkenyl And w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.9, and y + z is 0.1 to 1. And w + x + y + z = 1), provided that the silicone resin has an average of at least two silicon-bonded alkenyl groups per molecule.

The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R ¹ are free of aliphatic unsaturation and typically have 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms. . Acyclic hydrocarbyl groups and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of the hydrocarbyl group represented by R ¹ include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1 Alkyl such as ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl and decyl; cycloalkyl such as cyclopentyl, cyclohexyl and methylcyclohexyl; Aryls such as phenyl and naphthyl; alkaryls such as tolyl and xylyl; and aralkyls such as benzyl and phenethyl. Examples of the halogen-substituted hydrocarbyl group represented by R ¹ include 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3, Examples include, but are not limited to, 3-tetrafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl.

The alkenyl groups represented by R ^2, which may be the same or different, typically have from 2 to about 10 carbon atoms, alternatively 2 to 6 carbon atoms. Examples include but are not limited to vinyl, allyl, butenyl, hexenyl and octenyl.

  In the formula (I) of the silicone resin, the subscripts w, x, y, and z are mole fractions. The subscript w typically has a value from 0 to 0.95, alternatively from 0 to 0.8, alternatively from 0 to 0.2, and the subscript x typically from 0 to 0. .95, alternatively having a value from 0 to 0.8, alternatively from 0 to 0.5, the subscript y is typically 0 to 1, alternatively 0.3 to 1, Alternatively, it has a value between 0.5 and 1, and the subscript z is typically a value from 0 to 0.9, alternatively from 0 to 0.5, alternatively from 0 to 0.1. And the sum of y + z typically has a value of 0.1 to 1, alternatively 0.2 to 1, alternatively 0.5 to 1, alternatively 0.8 to 1. Have.

Typically, at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol% of the group R ² in the silicone resin is alkenyl. The term “mol% of the group R ² in the silicone resin is alkenyl” means that the ratio of the number of moles of silicon-bonded alkenyl groups in the silicone resin to the total number of moles of group R ^{2 in} the silicone resin is multiplied by 100. Defined as

Silicone resins are typically less than 10% (w / w), alternatively less than 5% (w / w), alternatively less than 2% (w / w) silicon as determined by ²⁹ Si NMR. Contains bound hydroxy groups.

Examples of silicone resins suitable for use as component (A) include:
(Vi ₂ MeSiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 , (ViMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 , (ViMe ₂ SiO _1/2 ) _0.25 (MeSiO _3/2 ) _0.25 (PhSiO _3/2 ) _0.50 , (ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.75 (SiO _4/2 ) _0.1 and (Vi ₂ MeSiO _1/2 ) _0.15 (ViMe ₂ SiO _1/2 ) _0.1 (PhSiO _3/2 ) _0.75
(Wherein Me is methyl, Vi is vinyl, Ph is phenyl, and the subscript number outside the brackets indicates the mole fraction), but is not limited thereto. In the above formula, the order of the units is not specified.

  Component (A) may be a single silicone resin, each as described above, or a mixture comprising two or more different silicone resins.

Methods for preparing silicone resins containing silicon-bonded alkenyl groups are known in the art and many of these resins are commercially available. These resins are typically prepared by cohydrolyzing a suitable mixture of chlorosilane precursors in an organic solvent such as toluene. For example, a silicone resin consisting essentially of R ¹ R ² ₂ SiO _1/2 and R ² SiO _3/2 units has a compound having the formula R ¹ R ² ₂ SiCl in toluene and the formula R ² SiCl ₃ . It can be prepared by cohydrolyzing the compound (wherein R ¹ and R ² are as defined and exemplified above). Separate the hydrochloric acid aqueous solution and the silicone hydrolyzate, wash the hydrolyzate with water to remove residual acid, and heat in the presence of a mild condensation catalyst to “thicken” the resin to the required viscosity. Let If necessary, the resin can be further treated with a condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups. Alternatively, containing _-Br, -I, and -OCH 3, -OC (O) CH 3, -N (CH 3) 2, NHCOCH 3 and -SCH _3, etc., other than chloro hydrolyzable group Silane can be utilized as a starting material in the cohydrolysis reaction. The properties of the resin product depend on the type of silane, the molar ratio of silane, the degree of condensation and the processing conditions.

  Component (B) is at least one organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule in an amount sufficient to cure the silicone resin of component (A).

  Organosilicon compounds have an average of at least two silicon-bonded hydrogen atoms per molecule, alternatively an average of at least three silicon-bonded hydrogen atoms per molecule. Generally, crosslinking occurs when the sum of the average number of alkenyl groups per molecule in component (A) and the average number of silicon-bonded hydrogen atoms per molecule in component (B) exceeds 4. To be understood.

  The organosilicon compound may be an organohydrogensilane or an organohydrogensiloxane. The organohydrogensilane may be monosilane, disilane, trisilane, or polysilane. Similarly, the organohydrogensiloxane may be a disiloxane, a trisiloxane, or a polysiloxane. The structure of the organosilicon compound may be linear, branched, cyclic or resinous. Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms. In acyclic polysilanes and polysiloxanes, silicon-bonded hydrogen atoms may be located at the terminal, side chain, or both terminal and side chain positions.

  Examples of organohydrogensilane include diphenylsilane, 2-chloroethylsilane, bis [(p-dimethylsilyl) phenyl] ether, 1,4-dimethyldisilylethane, 1,4-bis (dimethylsilyl) benzene, Examples include, but are not limited to, 1,3,5-tris (dimethylsilyl) benzene, 1,3,5-trimethyl-1,3,5-trisilane, poly (methylsilylene) phenylene and poly (methylsilylene) methylene. Not.

Examples of organohydrogensiloxanes include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris (dimethylsiloxy) silane, 1,3,5-trimethyl Cyclotrisiloxane, trimethylsiloxy-terminated poly (methylhydrogensiloxane), trimethylsiloxy-terminated poly (dimethylsiloxane / methylhydrogensiloxane), dimethylhydrogensiloxy-terminated poly (methylhydrogensiloxane), and essentially HMe ₂ SiO ₁ Examples include, but are not limited to, resins composed of _{/ 2} units, Me ₃ SiO _1/2 units, and SiO _4/2 units, where Me is methyl.

  Component (C) of the hydrosilylation-curable silicone composition is at least one hydrosilylation catalyst that promotes the addition reaction between component (A) and component (B). The hydrosilylation catalyst may be any of the known hydrosilylation catalysts, including platinum group metals, compounds containing platinum group metals, or microencapsulated platinum group metal-containing catalysts. Platinum group metals include platinum, rhodium, ruthenium, palladium, osmium and iridium. Preferably the platinum group metal is platinum based on its high activity in the hydrosilylation reaction.

  Preferred hydrosilylation catalysts include complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in US Pat. No. 3,419,593 (incorporated herein by reference). Is mentioned. A preferred catalyst of this type is the reaction product of platinic acid and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.

  The hydrosilylation catalyst may be a microencapsulated platinum group metal-containing catalyst comprising a platinum group metal encapsulated in a thermoplastic resin. Compositions containing microencapsulated hydrosilylation catalysts are stable for long periods of time under ambient conditions, typically several months or more, but are relatively rapid at temperatures above the melting point or softening point of the thermoplastic resin (s). To harden. Microencapsulated hydrosilylation catalysts and methods of preparing them are described in U.S. Pat. No. 4,766,176 and references cited therein, as exemplified in U.S. Pat. No. 5,017,654. Known in the technical field.

  Component (C) can be a single hydrosilylation catalyst or two or more different catalysts that differ in at least one property, such as structure, morphology, platinum group metal, complexing ligand and thermoplastic resin. It may be a mixture containing.

  The concentration of component (C) is sufficient to catalyze the addition reaction between component (A) and component (B). Typically, the concentration of component (C) is 0.1 to 1,000 ppm platinum group metal, preferably 1 to 500 ppm platinum group metal, based on the total weight of component (A) and component (B). More preferably at a concentration sufficient to provide 5-150 ppm of platinum group metal. The cure rate is very slow for platinum group metals of less than 0.1 ppm. The use of platinum group metals above 1,000 ppm is uneconomical because it results in a significant increase in the cure rate.

According to a second embodiment, the hydrosilylation curable silicone composition comprises (A ′) formula (R ¹ R ³ ₂ SiO _1/2 ) _w (R ³ ₂ SiO _2/2 ) _x (R ³ SiO _{3 / 2} ) _y (SiO _4/2 ) _z (II) (wherein each R ¹ is independently C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl, both free of aliphatic unsaturation) Each R ³ is independently R ¹ or —H, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, and z is 0. A silicone resin having an average of at least 2 silicon-bonded hydrogen atoms per molecule, with ~ 0.9, y + z being 0.1-1 and w + x + y + z = 1. B ′) an amount sufficient to cure the silicone resin, on average at least two silicon-bonded atoms per molecule Comprising an organic silicon compound having an alkenyl group, a hydrosilylation catalyst (C) a catalytic amount.

Component (A ′) has the formula (R ¹ R ³ ₂ SiO _1/2 ) _w (R ³ ₂ SiO _2/2 ) _x (R ³ SiO _3/2 ) _y (SiO _4/2 ) _z (II) ( Wherein each R ¹ is independently C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl (both free of aliphatic unsaturation) and each R ³ is independently R ¹ or -H, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.9, and y + z is 0.1 to 1. And w + x + y + z = 1), provided that the silicone resin has an average of at least two silicon-bonded hydrogen atoms per molecule. In formula (II), R ¹ , w, x, y, z and y + z are as described and exemplified above for the silicone resin having formula (I).

Typically, at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol% of the group R ³ in the silicone resin is hydrogen. The term “mol% of the group R ³ in the silicone resin is hydrogen” means that the ratio of the number of moles of silicon-bonded hydrogen atoms in the silicone resin to the total number of moles of the group R ^{3 in} the silicone resin is multiplied by 100. Defined as

Silicone resins are typically less than 10% (w / w), alternatively less than 5% (w / w), alternatively less than 2% (w / w) silicon as determined by ²⁹ Si NMR. Contains bound hydroxy groups.

Examples of silicone resins suitable for use as component (A ′) include:
(HMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 , (HMeSiO _2/2 ) _0.3 (PhSiO _3/2 ) _0.6 (MeSiO _3/2 ) _0.1 and (Me ₃ SiO _1/2 ) _0.1 (H ₂ SiO _2/2 ) _0.1 (MeSiO _3/2 ) _0.4 (PhSiO _3/2 ) _0.4
(Wherein, Me is methyl, Ph is phenyl, and the subscript number outside the parentheses indicates the mole fraction), but is not limited thereto. In the above formula, the order of the units is not specified.

  Component (A ') may be a single silicone resin, each as described above, or a mixture comprising two or more different silicone resins.

Methods for preparing silicone resins containing silicon-bonded hydrogen atoms are known in the art and many of these resins are commercially available. Silicone resins are typically prepared by cohydrolyzing a suitable mixture of chlorosilane precursors in an organic solvent such as toluene. For example, a silicone resin consisting essentially of R ¹ R ³ ₂ SiO _1/2 units and R ³ SiO _3/2 units has a compound having the formula R ¹ R ³ ₂ SiCl and the formula R ³ SiCl ₃ in toluene. It can be prepared by cohydrolyzing the compound (wherein R ¹ and R ³ are as described and exemplified above). The aqueous hydrochloric acid and silicone hydrolyzate are separated, the hydrolyzate is washed with water to remove residual acid, and heated in the presence of a mild non-basic condensation catalyst to bring the resin to the required viscosity. "Thickening". If desired, the resin can be further treated with an abasic condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups. Alternatively, containing _-Br, -I, and -OCH 3, -OC (O) CH 3, -N (CH 3) 2, NHCOCH 3 and -SCH _3, etc., other than chloro hydrolyzable group Silane can be utilized as a starting material in the cohydrolysis reaction. The properties of the resin product depend on the type of silane, the molar ratio of silane, the degree of condensation and the processing conditions.

  Component (B ') is at least one organosilicon compound having an average of at least two silicon-bonded alkenyl groups per molecule in an amount sufficient to cure the silicone resin of component (A').

  Organosilicon compounds contain an average of at least two silicon-bonded alkenyl groups per molecule, alternatively an average of at least three silicon-bonded alkenyl groups per molecule. When the sum of the average number of silicon-bonded hydrogen atoms per molecule in component (A ′) and the average number of silicon-bonded alkenyl groups per molecule in component (B ′) exceeds 4, It is generally understood when it happens.

  The organosilicon compound may be an organosilane or an organosiloxane. The organosilane may be monosilane, disilane, trisilane or polysilane. Similarly, the organosiloxane may be a disiloxane, trisiloxane or polysiloxane. The structure of the organosilicon compound may be linear, branched, cyclic or resinous. Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 5 silicon atoms. In acyclic polysilanes and polysiloxanes, silicon-bonded alkenyl groups may be located at the terminal, side chain, or both terminal and side chain positions.

Examples of organosilanes suitable for use as component (B ′) include:
Vi ₄ Si, PhSiVi ₃ , MeSiV ₃ , PhMeSiVi ₂ , Ph ₂ SiVi ₂ , and PhSi (CH ₂ CH═CH ₂ ) ₃
(Wherein Me is methyl, Ph is phenyl, and Vi is vinyl), but is not limited to.

Examples of organosiloxanes suitable for use as component (B ′) include:
PhSi (OSiMe ₂ Vi) ₃ , Si (OSiMe ₂ Vi) ₄ , MeSi (OSiMe ₂ Vi) ₃ , and Ph ₂ Si (OSiMe ₂ Vi) ₂
(Wherein Me is methyl, Ph is phenyl, and Vi is vinyl), but is not limited to.

  Component (B ') may be a single organosilicon compound, each as described above, or a mixture comprising two or more different organosilicon compounds. For example, component (B ′) may be a single organosilane, a mixture of two different organosilanes, a single organosiloxane, a mixture of two different organosiloxanes, or a mixture of organosilane and organosiloxane. Good.

  The concentration of component (B ′) is sufficient to cure (crosslink) the silicone resin of component (A ′). The exact amount of component (B ′) depends on the desired degree of cure and is the number of moles of silicon-bonded alkenyl groups in component (B ′) relative to the number of moles of silicon-bonded hydrogen atoms in component (A ′). As the ratio increases, it generally increases. The concentration of component (B ′) is typically from 0.4 moles to 2 moles of silicon-bonded alkenyl groups per mole of silicon-bonded hydrogen atoms in component (A ′), alternatively from 0.8 moles to 1 Sufficient to provide 5 moles of silicon-bonded alkenyl groups, alternatively 0.9 moles to 1.1 moles of silicon-bonded alkenyl groups.

  Methods for preparing organosilanes and organosiloxanes containing silicon-bonded alkenyl groups are known in the art and many of these compounds are commercially available.

  Component (C) of the second embodiment of the hydrosilylation curable silicone composition is similar to that described and exemplified above for component (C) of the first embodiment.

  The hydrosilylation curable silicone composition of the present method may include additional components that do not prevent the silicone composition from curing to form the first interfacial coating of the electronic package as described above. Examples of additional components include 3-methyl-3-penten-1-in, 3,5-dimethyl-3-hexen-1-in, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl Hydrosilylation catalyst inhibitors such as -1-cyclohexanol, 2-phenyl-3-butyn-2-ol, vinylcyclosiloxane and triphenylphosphine; US Pat. Nos. 4,087,585 and 5,194,649 Fixing agents such as fixing agents taught in No. 1, dyes, pigments, antioxidants, heat stabilizers, UV stabilizers, flame retardants, flow control agents, and diluents such as organic solvents and reactive diluents However, it is not limited to these.

  Condensation curable silicone compositions typically contain a silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups or hydrolyzable groups per molecule, and optionally silicon-bonded hydrolyzable groups. A crosslinking agent and / or a condensation catalyst.

According to one embodiment, the condensation curable silicone composition has the formula (R ⁴ R ⁵ ₂ SiO _1/2 ) _w (R ⁵ ₂ SiO _2/2 ) _x (R ⁵ SiO _3/2 ) _y (SiO _{4 / 2} ) _z (III) (wherein each R ⁴ is independently C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl, and each R ⁵ is independently R ⁴ , —H , —OH or a hydrolyzable group, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.9, and y + z. In the range of 0.1 to 1 and w + x + y + z = 1), provided that the silicone resin averages at least two silicon-bonded hydrogen atoms, hydroxy groups or hydrolysable per molecule Group). In formula (III), w, x, y, z and y + z are as described and exemplified above for the silicone resin having formula (I).

The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R ⁴ are typically 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms. Has carbon atoms. Acyclic hydrocarbyl groups and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2- Alkyl such as methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl and decyl; cycloalkyl such as cyclopentyl, cyclohexyl and methylcyclohexyl; aryl such as phenyl and naphthyl Alkaryl such as tolyl and xylyl; aralkyl such as benzyl and phenethyl; alkenyl such as vinyl, allyl and propenyl; aryl alkenyl such as styryl and cinnamyl; and alkynyl such as ethynyl and propynyl; But, but it is not limited to these. Examples of halogen-substituted hydrocarbyl groups include 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, And 2,2,3,3,4,4,5,5-octafluoropentyl, but is not limited thereto.

As used herein, the term “hydrolyzable group” refers to room temperature (about 23 ± 2 ° C.) to 100 ° C. for several minutes, for example 30 minutes, in the presence or absence of a catalyst. It means a silicon-bonded group that reacts with water underneath to form a silanol (Si—OH) group. Examples of the hydrolyzable group represented by R ⁵ include —Cl, —Br, —OR ⁶ , —OCH ₂ CH ₂ OR ⁶ , CH ₃ C (═O) O—, Et (Me) C═N. _{-O-, CH 3 C (= O} ) N (CH 3) - and -ONH ₂ (wherein, R ⁶ is C ₁ -C ₈ hydrocarbyl or C ₁ -C ₈ halogen substituted hydrocarbyl) but may be mentioned However, it is not limited to these.

The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R ⁶ typically have 1 to 8 carbon atoms, alternatively 3 to 6 carbon atoms. Acyclic hydrocarbyl groups and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl Unbranched and branched alkyl such as 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl and octyl; cycloalkyl such as cyclopentyl, cyclohexyl and methylcyclohexyl; phenyl; tolyl And alkaryl such as benzyl and phenethyl; alkenyl such as vinyl, allyl and propenyl; aryl alkenyl such as styryl; and alkynyl such as ethynyl and propynyl. Examples of halogen-substituted hydrocarbyl groups include, but are not limited to 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl and dichlorophenyl.

Typically, at least 10 mol%, alternatively at least 50 mol%, alternatively at least 80 mol% of the groups R ⁵ in the silicone resin are hydrogen, hydroxy groups or hydrolyzable groups. The term “mol% of the group R ⁵ in the silicone resin is hydrogen, a hydroxy group or a hydrolyzable group” means the silicon-bonded hydrogen in the silicone resin relative to the total number of moles of the group R ^{5 in} the silicone resin, Defined as 100 times the ratio of the number of moles of hydroxy or hydrolyzable groups.

Examples of silicone resins having formula (III) include:
(MeSiO _3/2 ) _n , (PhSiO _3/2 ) _n , (Me ₃ SiO _1/2 ) _0.8 (SiO _4/2 ) _0.2 , (MeSiO _3/2 ) _0.67 (PhSiO _3/2 ) _0.33 , (MeSiO _3/2 ) _0.45 (PhSiO _3/2 ) _0.40 (Ph ₂ SiO _2/2 ) _0.1 (PhMeSiO _2/2 ) _0.05 , (PhSiO _3/2 ) _0.4 (MeSiO _3/2 ) _0.45 (PhSiO _3/2 ) _0.1 (PhMeSiO _2/2 ) _0.05 and (PhSiO _3/2 ) _0.4 (MeSiO _3/2 ) _0.1 (PhMeSiO _2/2 ) _0.5
(In the formula, Me is methyl, Ph is phenyl, the subscript number outside the parentheses indicates the mole fraction, and the subscript n is a weight average of 500 to 1,000,000 of the silicone resin. Resin having a value having a molecular weight), but is not limited thereto. In the above formula, the order of the units is not specified.

  The condensation curable silicone composition may comprise a single silicone resin, or a mixture comprising two or more different silicone resins, each as described above.

Methods for preparing silicone resins containing silicon-bonded hydrogen atoms, hydroxy groups or hydrolyzable groups are known in the art and many of these resins are commercially available. Silicone resins are typically prepared by cohydrolyzing a suitable mixture of silane precursors in an organic solvent such as toluene. For example, a silicone resin can be prepared by cohydrolyzing a silane having the formula R ⁴ R ⁵ ₂ SiX and a silane having the formula R ⁵ SiX ₃ in toluene (wherein R ⁴ is C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl, R ⁵ is R ⁴ , —H or a hydrolyzable group, and X is a hydrolyzable group, provided that R ⁵ is When it is a hydrolyzable group, X is more reactive in the hydrolysis reaction than R ⁵ ). Separate the hydrochloric acid aqueous solution and the silicone hydrolyzate, wash the hydrolyzate with water to remove residual acid, and heat in the presence of a mild condensation catalyst to “thicken” the resin to the required viscosity. (Ie condensation). If necessary, the resin can be further treated with a condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups.

  The condensation curable silicone composition may include additional components that do not prevent the silicone resin from curing to form the first interfacial coating of the electronic package as described above. Examples of additional components include fixing agents, dyes, pigments, antioxidants, heat stabilizers, UV stabilizers, flame retardants, flow control agents, and organic solvents, crosslinking agents and condensation catalysts. It is not limited to.

For example, the condensation curable silicone composition may further contain a crosslinking agent and / or a condensation catalyst. The cross-linking agent is of the formula R ⁶ _q SiX _{4-q where} R ⁶ is a C ₁ -C ₈ hydrocarbyl or C ₁ -C ₈ halogen-substituted hydrocarbyl, X is a hydrolyzable group and q is 0 or 1). The hydrocarbyl group and halogen-substituted hydrocarbyl group represented by R ⁶ are as described and exemplified above. The hydrolyzable group represented by X is as described and exemplified above for R ⁵ .

Examples of the crosslinking agent include MeSi (OCH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₂ CH ₃ ) ₃ , CH ₃ Si [O (CH ₂ ) ₃ CH ₃ ] ₃ , CH ₃ CH ₂ Si (OCH ₂ CH ₃ ) ₃ , C ₆ H ₅ Si (OCH ₃ ) ₃ , C ₆ H ₅ CH ₂ Si (OCH ₃ ) ₃ , C ₆ H ₅ Si (OCH ₂ CH _{3 ) 3, CH 2 = CHSi (} OCH 3) 3, CH 2 = CHCH 2 Si (OCH 3) 3, CF 3 CH 2 CH 2 Si (OCH 3) 3, CH 3 Si (OCH 2 CH 2 OCH 3) 3 _{, CF 3 CH 2 CH 2 Si} (OCH 2 CH 2 OCH 3) 3, CH 2 = CHSi (OCH 2 CH 2 OCH 3) 3, CH 2 = CHCH 2 Si (OCH 2 CH 2 OCH 3) 3, C 6 _{H 5 Si (OCH 2 CH 2} OCH 3) 3, Si (OCH 3) 4, Si (OC 2 H 5) 4 Alkoxysilanes such as and _{Si (OC 3 H 7) 4} ; CH 3 Si (OCOCH 3) 3, CH 3 CH 2 Si (OCOCH 3) 3 and CH ₂ = CHSi organosilane acetoxysilane such as (OCOCH _{3) 3;} CH ₃ Si [O—N═C (CH ₃ ) CH ₂ CH ₃ ] ₃ , Si [O—N═C (CH ₃ ) CH ₂ CH ₃ ] ₄ and CH ₂ ═CHSi [O—N═C (CH ₃ ) Organoiminooxysilane such as CH ₂ CH ₃ ] ₃ ; Organoacetamide silane such as CH ₃ Si [NHC (═O) CH ₃ ] ₃ and C ₆ H ₅ Si [NHC (═O) CH ₃ ] ₃ ; CH Examples include, but are not limited to, aminosilanes such as ₃ Si [NH (s-C ₄ H ₉ )] ₃ and CH ₃ Si (NHC ₆ H ₁₁ ) ₃ ; and organoaminooxysilanes.

  The cross-linking agent may be a single silane, each as described above, or a mixture comprising two or more different silanes. Also, methods for preparing trifunctional and tetrafunctional silanes are known in the art, and many of these silanes are commercially available.

  When present, the concentration of the crosslinking agent in the silicone composition is sufficient to cure (crosslink) the silicone resin. The exact amount of crosslinker depends on the desired degree of cure, which is the silicon bond hydrolyzable groups in the crosslinker relative to the number of moles of silicon bonded hydrogen atoms, hydroxy groups or hydrolyzable groups in the silicone resin. As the ratio of moles increases, it generally increases. Typically, the concentration of the crosslinker is sufficient to provide 0.2 to 4 moles of silicon-bonded hydrolyzable groups per mole of silicon-bonded hydrogen atoms, hydroxy groups or hydrolyzable groups in the silicone resin. Is something. The optimal amount of cross-linking agent can be readily determined by routine experimentation.

  As mentioned above, the condensation curable silicone composition may further comprise at least one condensation catalyst. The condensation catalyst may be any condensation catalyst typically used to promote the condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si bonds. Examples of condensation catalysts include, but are not limited to, amines; and complexes of lead, tin, zinc and iron with carboxylic acids. In particular, the condensation catalyst can be selected from tin (II) compounds and tin (IV) compounds such as tin dilaurate, tin dioctanoate and tetrabutyltin; and titanium compounds such as titanium tetrabutoxide.

  When present, the concentration of condensation catalyst is typically 0.1% (w / w) to 10% (w / w), alternatively 0.5% (w / w), based on the total weight of the silicone resin. w) to 5% (w / w), alternatively 1% (w / w) to 3% (w / w).

  The radiation curable silicone composition typically comprises a silicone resin having an average of at least two silicon-bonded radiation sensitive groups per molecule, and optionally a photoinitiator.

According to one embodiment, the radiation curable silicone composition has the formula (R ⁷ R ⁸ ₂ SiO _1/2 ) _w (R ⁸ ₂ SiO _2/2 ) _x (R ⁸ SiO _3/2 ) _y (SiO _{4 / 2} ) _z (IV) (wherein each R ⁷ is independently C ₁ -C ₁₀ hydrocarbyl, C ₁ -C ₁₀ halogen-substituted hydrocarbyl, or —OR ⁶ , wherein R ⁶ is C _{1 to} C ₈ hydrocarbyl or C _{1 to} C ₈ halogen-substituted hydrocarbyl), each R ⁸ is independently R ¹ , —H or a radiation sensitive group, and w is 0 to 0.95. , X is 0 to 0.95, y is 0 to 1, z is 0 to 0.9, y + z is 0.1 to 1, and w + x + y + z = 1). (However, the silicone resin has an average of at least two silicon-bonded radiation sensitive molecules per molecule. Having a group). In the formula (IV), R ⁶ , w, x, y, z and y + z are as described and exemplified above. The hydrocarbyl group and halogen-substituted hydrocarbyl group represented by R ⁷ are as described and exemplified above for R ⁴ .

Examples of radiation sensitive groups represented by R ⁸ include, but are not limited to, acryloyloxyalkyl, substituted acryloyloxyalkyl, alkenyl ether groups, alkenyl, and epoxy substituted organic groups. As used herein, the term “radiation sensitive group” refers to the presence of a free radical photoinitiator or a cationic photoinitiator when exposed to radiation having a wavelength of 150 nm to 800 nm. By groups that form reactive species (eg free radicals or cations).

Examples of acryloyloxyalkyl groups represented by R ⁸ include, but are not limited to, acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, and 4-acryloyloxybutyl.

Examples of substituted acryloyloxyalkyl groups represented by R ⁸ include, but are not limited to, methacryloyloxymethyl, 2-methacryloyloxyethyl, and 3-methacryloyloxypropyl.

Examples of the alkenyl ether group represented by R ⁸ include the formula —O—R ⁹ —O—CH═CH ₂ (wherein R ⁹ is C ₁ -C ₁₀ hydrocarbylene or C ₁ -C ₁₀ halogen). Vinyl ether groups having, but not limited to, substituted hydrocarbylene).

The hydrocarbylene group represented by R ⁹ typically has 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms. Have. Examples of hydrocarbylene groups include methylene, ethylene, propane-1,3-diyl, 2-methylpropane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl, pentane- Alkylene such as 1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, and decane-1,10-diyl; cyclohexane-1,4-diyl, etc. And arylenes such as phenylene, but are not limited thereto. Examples of halogen-substituted hydrocarbylene groups include divalent hydrocarbon groups in which one or more hydrogen atoms are replaced by halogens such as fluorine, chlorine and bromine (for example, —CH ₂ CH ₂ CF ₂ CF ₂ CH ₂ CH ₂ -) include, but are not limited to.

Examples of alkenyl groups represented by R ⁸ include, but are not limited to, vinyl, allyl, propenyl, butenyl and hexenyl.

As used herein, the term “epoxy-substituted organic group” refers to a monovalent organic group in which an epoxy substituent that is an oxygen atom is directly bonded to two adjacent carbon atoms of a carbon chain or ring system. Point to. Examples of the epoxy-substituted organic group represented by R ⁸ include 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, 2- (3,4-epoxycyclohexyl) ethyl, 3- (3,4-epoxycyclohexyl) propyl, 2- (3,4-epoxy-3-methylcyclohexyl) -2-methylethyl , 2- (2,3-epoxycyclopentyl) ethyl, and 3- (2,3-epoxycyclopentyl) propyl, but are not limited to these.

Silicone resins typically contain an average of at least two silicon-bonded radiation sensitive groups per molecule. Generally, at least 50 mol%, alternatively at least 65 mol%, alternatively at least 80 mol% of the groups R ⁸ in the silicone resin are radiation sensitive groups. The term “mol% of the group R ⁸ in the silicone resin is a radiation-sensitive group” means the number of moles of silicon-bonded radiation-sensitive groups in the silicone resin relative to the total number of moles of the group R ^{8 in} the silicone resin. It is defined as the ratio multiplied by 100.

  Examples of silicone resins having the formula (IV) include the following formula:

(Wherein Me is methyl, Ph is phenyl, Vi is vinyl, and the subscript number outside the brackets indicates the mole fraction), but is not limited thereto. In the above formula, the order of the units is not specified.

  Methods for preparing silicone resins having silicon-bonded radiation sensitive groups are known in the art. For example, silicone resins containing silicon-bonded acryloyloxyalkyl groups or substituted acryloyloxyalkyl groups can be used as acidic catalysts or as illustrated in US Pat. Nos. 5,738,976 and 5,959,038. It can be prepared by cohydrolyzing acryloyloxyalkyl- or substituted acryloyloxyalkylalkoxysilane and alkoxysilane in the presence of a basic catalyst. Alternatively, such resins may be co-hydrolyzed of acryloyloxyalkyl- or substituted acryloyloxayalkylchlorosilane and at least one chlorosilane as taught in US Pat. No. 4,568,566. Can be generated.

Silicone resins containing silicon-bonded alkenyl ether groups are prepared by reacting an alkoxysilane with water in the presence of an acidic condensation catalyst, as described in US Pat. No. 5,861,467, after which the reaction mixture is hydroxylated. It can be prepared by treatment with a substituted vinyl ether and a transesterification catalyst. Briefly, the method comprises the step of reacting a silane, the (b) water, and (c) an acidic condensation catalyst having (I) (a) formula ^{_{R x Si (OR 1) 4}} -x, (II ) A step of removing alcohol from the mixture of step (I), (III) a step of neutralizing the mixture of step (II), and (IV) a vinyl ether compound having the formula HO—R ² —O—CH═CH ₂ (V) adding a transesterification catalyst to the mixture of step (IV), and (VI) removing volatiles from the mixture of step (V), wherein R is 1 is a monovalent hydrocarbon radical or halohydrocarbon radical having 1 to 20 carbon atoms, R ¹ is a monovalent alkyl radical having 1 to 8 carbon atoms, and R ² is 1 A divalent hydrocarbon radical or halo having from 20 to 20 carbon atoms Hydrocarbon radicals and x has a value of 0 to 3) (provided that the molar ratio of water to alkoxy radicals is less than 0.5).

Alternatively, a silicone resin containing alkenyl ether groups can be obtained from alkoxysilane, water, and hydroxy-substituted vinyl ether compounds in the presence of a non-acidic condensation catalyst, as described in US Pat. No. 5,824,761. And then treating the reaction mixture with a transesterification catalyst. Briefly, this method, (I) (a) formula ^{_{R x Si (OR 1) 4}} -x, (b) water, (c) a carboxylic acid amine, carboxylic acid heavy metal, isocyanates, silanolates, phenoxides, mercaptides Reacting a non-acidic condensation catalyst selected from CaO, BaO, LiOH, BuLi, amine and ammonium hydroxide, and (d) a vinyl ether compound having the formula HO—R ² —O—CH═CH ₂ , (II ) Removing alcohol from the mixture of (I), neutralizing the mixture of (III) (II), (IV) adding a transesterification catalyst to the mixture of (III), and (V) (IV (wherein comprises removing volatiles from the mixture of), R is a monovalent hydrocarbon radical or halohydrocarbon radical having 1 to 20 carbon atoms, R ¹ Is a monovalent alkyl radical having 1 to 8 carbon atoms, R ² is a divalent hydrocarbon radical or halohydrocarbon radical having 1 to 20 carbon atoms, and x is 0 3) (provided that the molar ratio of water to alkoxy radicals is less than 0.5).

  Silicone resins containing silicon-bonded alkenyl groups can be prepared similarly to those described above for silicone resins having the formula (I).

  Silicone resins containing silicon-bonded epoxy-substituted organic groups can be prepared by co-hydrolyzing an epoxy-functional alkoxysilane and an alkoxysilane in the presence of an organotitanic acid catalyst as described in US Pat. No. 5,468,826. It can be prepared by decomposing. Alternatively, silicone resins containing silicon-bonded epoxy-substituted organic groups are described in US Pat. Nos. 6,831,145, 5,310,843, 5,530,075, As described in US Pat. Nos. 283,309, 5,468,827, 5,486,588 and 5,358,983, silicon-bonded hydrogen atoms are present in the presence of a hydrosilylation catalyst. Can be prepared by reacting an epoxy functional alkene.

  The radiation curable silicone composition may include additional components that do not prevent the silicone resin from curing to form the first interfacial coating of the electronic package as described above. Examples of additional components include fixing agents, dyes, pigments, antioxidants, heat stabilizers, flame retardants, flow control agents, fillers (including bulking fillers and reinforcing fillers), organic solvents, crosslinking agents and photoinitiators. However, it is not limited to these.

  For example, the radiation curable silicone composition may further comprise at least one photoinitiator. The photoinitiator may be a cationic photoinitiator or a free radical photoinitiator depending on the nature of the radiation sensitive group in the silicone resin. For example, if the resin contains alkenyl ether groups or epoxy-substituted organic groups, the silicone composition can further include at least one cationic photoinitiator. The cationic photoinitiator can be any cationic photoinitiator that can cure (cross-link) the silicone resin upon exposure to radiation having a wavelength of 150 nm to 800 nm. Examples of cationic photoinitiators include onium salts, diaryl iodonium salts of sulfonic acids, triaryl sulfonium salts of sulfonic acids, diaryl iodonium salts of boronic acids, and triarylsulfonium salts of boronic acids. It is not limited.

Suitable onium salts include R ¹⁰ ₂ I ⁺ MX _z ⁻ , R ¹⁰ ₃ S ⁺ MX _z ⁻ , R ¹⁰ ₃ Se ⁺ MX _z ⁻ , R ¹⁰ ₄ P ⁺ MX _z ⁻ , and R ¹⁰ ₄ N ⁺ MX. _z ⁻ (wherein each R ¹⁰ is independently a hydrocarbyl or substituted hydrocarbyl having 1 to 30 carbon atoms, and M is selected from transition metals, rare earth metals, lanthanide metals, metalloids, phosphorus and sulfur. X is halo (eg, chloro, bromo, iodo) and z is selected from the product z (charge of X + number of oxidations of M) = − 1) And salts having the formula: Examples of substituents on the hydrocarbyl group, C ₁ -C ₈ alkoxy, C ₁ -C ₁₆ alkyl, nitro, chloro, bromo, cyano, carboxyl, mercapto, and pyridyl, heterocyclic aromatic, such as thiophenyl and pyranyl Groups, but not limited to. Examples of metals represented by M include transition metals such as Fe, Ti, Zr, Sc, V, Cr and Mn; lanthanide metals such as Pr and Nd; Cs, Sb, Sn, Bi, Al, Ga and In Other metals such as, but not limited to, metalloids such as B and As; and P. The formula MXz ⁻ represents a non-basic, non-nucleophilic anion. Examples of anions having the formula MXz ⁻ include, but are not limited to, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ and SnCl ₆ ⁻ .

  Examples of onium salts include bis-diaryl iodonium salts such as bis (dodecylphenyl) iodonium hexafluoroarsenate, bis (dodecylphenyl) iodonium hexafluoroantimonate, and dialkylphenyliodonium hexafluoroantimonate. It is not limited to.

  Examples of diaryl iodonium salts of sulfonic acids include perfluorobutane sulfonic acid diaryl iodonium salts, perfluoroethane sulfonic acid diaryl iodonium salts, perfluorooctane sulfonic acid diaryl iodonium salts, and trifluoromethane sulfonic acid diaryl iodonium salts. Diaryl iodonium salts of alkyl sulfonic acids; and aryls such as diaryl iodonium salts of para-toluenesulfonic acid, diaryl iodonium salts of dodecylbenzene sulfonic acid, diaryl iodonium salts of benzene sulfonic acid, and diaryl iodonium salts of 3-nitrobenzene sulfonic acid Examples include, but are not limited to, diaryl iodonium salts of sulfonic acids.

  Examples of triarylsulfonium salts of sulfonic acids include triarylsulfonium salts of perfluorobutanesulfonic acid, triarylsulfonium salts of perfluoroethanesulfonic acid, triarylsulfonium salts of perfluorooctanesulfonic acid, and triaryl of trifluoromethanesulfonic acid Triarylsulfonium salts of perfluoroalkylsulfonic acids such as sulfonium salts; and triarylsulfonium salts of para-toluenesulfonic acid, triarylsulfonium salts of dodecylbenzenesulfonic acid, triarylsulfonium salts of benzenesulfonic acid, and 3-nitrobenzene Examples include, but are not limited to, triarylsulfonium salts of arylsulfonic acids such as triarylsulfonium salts of sulfonic acids.

  Examples of diaryl iodonium salts of boronic acids include, but are not limited to, diaryl iodonium salts of perhaloaryl boronic acids. Examples of triarylsulfonium salts of boronic acids include, but are not limited to, triarylsulfonium salts of perhaloarylboronic acids. Diaryl iodonium salts of boronic acids and triarylsulfonium salts of boronic acids are known in the art, as illustrated in EP 0562922.

  The cationic photoinitiator can be a single cationic photoinitiator, each as described above, or a mixture comprising two or more different cationic photoinitiators. The concentration of the cationic photoinitiator is typically 0.01% (w / w) to 20% (w / w), alternatively 0.1% (w / w) based on the weight of the silicone resin -20% (w / w), alternatively 0.1% -5%.

  When the silicone resin contains an acryloyloxyalkyl group, a substituted acryloyloxyalkyl group or an alkenyl group, the silicone composition can further comprise at least one free radical photoinitiator. The free radical photoinitiator can be any free radical photoinitiator that can initiate curing (crosslinking) of the silicone resin upon exposure to radiation having a wavelength of 150 nm to 800 nm.

  Examples of free radical photoinitiators include: benzophenone; 4,4′-bis (dimethylamino) benzophenone; halogenated benzophenone; acetophenone; α-hydroxyacetophenone; chloroacetophenone such as dichloroacetophenone and trichloroacetophenone; Dialkoxyacetophenones such as ethoxyacetophenone; α-hydroxyalkylphenones such as 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexyl phenyl ketone; 2-methyl-4 ′-(methylthio) -2 Α-aminoalkylphenones such as morpholinopropiophenone; benzoins; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isobutyl ether; 2 Benzyl ketals such as 2-dimethoxy-2-phenylacetophenone; acylphosphine oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; xanthone derivatives; thioxanthone derivatives; fluorenone derivatives; methylphenylglyoxylate; acetonaphthone; Quininone derivatives; sulfonyl chlorides of aromatic compounds; and O-acyl α-oximino ketones such as 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. It is not limited.

  Free radical photoinitiators are described in U.S. Pat. No. 4,260,780 (incorporated herein by reference), phenylmethylpolysilane as defined by West, U.S. Pat. No. 4,314,956 (incorporated by reference). Aminated methylpolysilane as defined by Baney et al., Incorporated herein by reference), Peterson et al. Methylpolysilane in US Pat. No. 4,276,424 (incorporated herein by reference), and US Pat. It may be a polysilane such as polysilastyrene as defined by West et al. In US Pat. No. 4,324,901 (incorporated herein by reference).

  The free radical photoinitiator may be a single free radical photoinitiator or a mixture comprising two or more different free radical photoinitiators. The concentration of free radical photoinitiator is typically 0.1% (w / w) to 20% (w / w), alternatively 1% (w / w) to 10 based on the weight of the silicone resin. % (W / w).

  Peroxide curable silicone compositions typically comprise a silicone resin having silicon-bonded unsaturated groups and an organic peroxide.

According to one embodiment, the peroxide curable silicone composition has the formula (R ¹ R ¹¹ ₂ SiO _1/2 ) _w (R ¹¹ ₂ SiO _2/2 ) _x (R ¹¹ SiO _3/2 ) _y ( SiO _4/2 ) _z (V), wherein each R ¹ is independently C ₁ -C ₁₀ hydrocarbyl or C ₁ -C ₁₀ halogen-substituted hydrocarbyl (both free of aliphatic unsaturation); R ¹¹ is independently R ¹ , alkenyl, alkynyl, acryloxyalkyl or substituted acryloxyalkyl, w is 0 to 0.95, x is 0 to 0.95, and y is 0 to 1. And z is 0 to 0.9, y + z is 0.1 to 1, and w + x + y + z = 1), and an organic peroxide. In formula (V), R ¹ , w, x, y, z and y + z are as described and exemplified above for the silicone resin having formula (I).

The alkenyl groups represented by R ^11, which may be the same or different, typically have 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, and vinyl , Allyl, butenyl, hexenyl and octenyl, but are not limited thereto.

The alkynyl group represented by R ^11, which may be the same or different, typically has 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, and ethynyl , Propynyl, butynyl, hexynyl and octynyl, but are not limited thereto

  In one embodiment of the silicone resin, the resin contains an average of at least one alkenyl or alkynyl group per molecule.

Silicone resins are typically less than 10% (w / w), alternatively less than 5% (w / w), alternatively less than 2% (w / w) silicon as determined by ²⁹ Si NMR. Contains bound hydroxy groups.

Examples of silicone resins having the formula (V) include the following formula:
(Vi ₂ MeSiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 , (ViMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 , (ViMe ₂ SiO _1/2 ) _0.25 (MeSiO _3/2 ) _0.25 (PhSiO _3/2 ) _0.50 , (ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.75 (SiO _4/2 ) _0.1 and (Vi ₂ MeSiO _1/2 ) _0.15 (ViMe ₂ SiO _1/2 ) _0.1 (PhSiO _3/2 ) _0.75
(Wherein Me is methyl, Vi is vinyl, Ph is phenyl, and the subscript number outside the brackets indicates the mole fraction), but is not limited thereto. In the above formula, the order of the units is not specified.

  The silicone resin may be a single silicone resin, each as described above, or a mixture comprising two or more different silicone resins.

Methods for preparing silicone resins having silicon-bonded alkenyl groups or silicon-bonded alkynyl groups are known in the art, and many of these resins are commercially available. These resins are typically prepared by cohydrolyzing a suitable mixture of chlorosilane precursors in an organic solvent such as toluene. For example, a silicone resin consisting essentially of R ¹ R ¹¹ ₂ SiO _1/2 and R ¹¹ SiO _3/2 units has a compound having the formula R ¹ R ¹¹ ₂ SiCl in toluene and the formula R ¹¹ SiCl ₃ . It can be prepared by cohydrolyzing the compound (wherein R ¹ and R ¹¹ are as defined and exemplified above). Separate the hydrochloric acid aqueous solution and the silicone hydrolyzate, wash the hydrolyzate with water to remove residual acid, and heat in the presence of a mild condensation catalyst to “thicken” the resin to the required viscosity. Let If necessary, the resin can be further treated with a condensation catalyst in an organic solvent to reduce the content of silicon-bonded hydroxy groups. Alternatively, containing _-Br, -I, and -OCH 3, -OC (O) CH 3, -N (CH 3) 2, NHCOCH 3 and -SCH _3, etc., other than chloro hydrolyzable group Silane can be utilized as a starting material in the cohydrolysis reaction. The properties of the resin product depend on the type of silane, the molar ratio of silane, the degree of condensation and the processing conditions.

  Examples of organic peroxides include diaroyl peroxides such as dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, and bis-2,4-dichlorobenzoyl peroxide; di-t-butyl peroxide and 2,5-dimethyl- Dialkyl peroxides such as 2,5-di- (t-butylperoxy) hexane; Diaralkyl peroxides such as dicumyl peroxide; Alkyls such as t-butylcumyl peroxide and 1,4-bis (t-butylperoxyisopropyl) benzene Aralkyl peroxides; and alkylaroyl peroxides such as t-butyl perbenzoate, t-butyl peracetate and t-butyl peroctoate.

  The organic peroxide can be a single peroxide or a mixture comprising two or more different organic peroxides. The concentration of organic peroxide is typically from 0.1% (w / w) to 5% (w / w), alternatively from 0.2% (w / w), based on the weight of the silicone resin. 2% (w / w).

  The peroxide curable silicone composition of the present invention may include additional components that do not prevent the silicone resin of the silicone composition from curing to form the first interfacial coating of the electronic package as described above. Examples of additional components include silicone rubbers, polyunsaturated compounds, free radical initiators, organic solvents, UV stabilizers, sensitizers, dyes, flame retardants, antioxidants, fillers (eg, reinforcing fillers, bulking fillers) And conductive fillers), and fixing agents, but are not limited thereto.

  During step (i) of the first method of forming the first interfacial coating, inkjet printing, screen printing, stencil printing, flexographic printing, lithography, gravure printing, soft lithography, xerography, imprinting (embossing), micro The curable silicone composition can be applied over the first inorganic barrier coating in the upper region of the electronic device using conventional printing methods such as dispensing, friction transfer printing, laser transfer printing, and thermal transfer printing. . The particular method chosen will depend on several factors including the rheology of the silicone composition, the desired thickness of the coating, the application temperature, and the desired resolution. The amount of silicone composition is sufficient to form a cured silicone resin film having a thickness of 0.06 to 30 μm in method step (ii) as described below.

  During step (ii) of the first method of preparing the first interfacial coating, the silicone resin of the membrane is cured. Depending on the type of curable silicone composition applied over the first inorganic barrier coating, the silicone resin of the film can be cured by exposing the film to ambient temperature, elevated temperature, moisture, or radiation.

  When the silicone composition applied over the first inorganic barrier coating is a hydrosilylation curable silicone composition, the silicone resin is at room temperature (about 23 ± 2 ° C.) to 250 ° C., alternatively Curing can be accomplished by heating the resin to room temperature to 200 ° C, alternatively to room temperature to 150 ° C. The resin shall be heated for a time sufficient to cure (crosslink) the silicone resin. For example, the resin is typically heated at a temperature of 150 ° C. to 200 ° C. for 0.1 hour to 3 hours.

  When the silicone composition applied on the first inorganic barrier coating is a condensation curable silicone composition, the conditions for curing the silicone resin depend on the nature of the silicon bonding groups in the resin. For example, if the silicone resin contains silicon-bonded hydroxy groups, the silicone resin can be cured (ie, crosslinked) by heating the membrane. For example, silicone resins can typically be cured by heating the membrane at a temperature of 50 ° C. to 250 ° C. for 1 hour to 50 hours. When the condensation curable silicone composition includes a condensation catalyst, the silicone resin can typically be cured at a lower temperature, such as room temperature (about 23 ± 2 ° C.) to 200 ° C.

  When the silicone resin contains silicon-bonded hydrogen atoms, the silicone resin can be cured by exposing the membrane to moisture or oxygen at a temperature of 100 ° C. to 450 ° C. for 0.1 hour to 20 hours. When the condensation curable silicone composition contains a condensation catalyst, the silicone resin can typically be cured at lower temperatures, for example, room temperature (about 23 ± 2 ° C.) to 400 ° C.

  In addition, when the silicone resin contains silicon-bonded hydrolyzable groups, the silicone resin is from room temperature (about 23 ± 2 ° C.) to 250 ° C., alternatively from 100 ° C. to 200 ° C. for 1 hour to 100 hours, The film can be cured by exposing it to moisture. For example, silicone resins can typically be cured by exposing the film to 30% relative humidity at a temperature of about room temperature (about 23 ± 2 ° C.) to 150 ° C. for 0.5 hours to 72 hours. Curing can be facilitated by heating, exposure to high humidity, and / or the addition of a condensation catalyst to the composition.

If the silicone composition applied over the first inorganic barrier coating is a radiation curable silicone composition, the silicone resin can be cured by exposing the film to an electron beam. Typically, the acceleration voltage is about 0.1 keV to 100 keV, the degree of vacuum is about 10 Pa to 10 ⁻³ Pa, the electron current is about 0.0001 amps to 1 amp, and the power is about 0.1 It varies from watts to 1 kilowatt. The dose is typically about 100 microcoulombs / cm ^{2 to} 100 coulombs / cm ² , alternatively about 1 coulombs / cm ² to 10 coulombs / cm ² . Depending on the voltage, the exposure time is typically about 10 seconds to 1 hour.

In addition, when the silicone composition further includes a cationic photoinitiator or a free radical photoinitiator as described above, the silicone resin has a dose sufficient to cure (crosslink) the silicone resin at 150 nm to 800 nm. Alternatively, it can be cured by exposing the film to radiation having a wavelength of 200 nm to 400 nm. The light source is typically a medium pressure mercury lamp. Dose of radiation ^{typically, 30mJ / cm 2 ~1,000mJ / cm} 2, alternatively a ^{50mJ / cm 2 ~500mJ / cm 2} . Moreover, the film can be externally heated during or after exposure to radiation to increase the cure rate and / or degree of cure.

  When the silicone composition applied on the first inorganic barrier coating is a peroxide curable silicone composition, the silicone resin may be from room temperature (about 23 ± 2 ° C.) to 180 ° C. for 0.05 hours to The film can be cured by heating for 1 hour.

  When the first interfacial coating is a cured product of a silicone resin having radiation sensitive groups, the first interfacial coating is (i) on the first inorganic barrier coating on average at least 2 per molecule. Applying a radiation curable silicone composition comprising a silicone resin having two silicon-bonded radiation-sensitive groups to form a film; (ii) in the upper region of an electronic device, film on radiation having a wavelength of 150 nm to 800 nm Exposing the substrate to create a partially exposed film having at least one exposed area and at least one unexposed area; and (iii) removing the unexposed area of the heated film with a developing solvent. The first photolithographic method can include forming a patterned film.

  During step (i) of the first photolithography method, inkjet printing, screen printing, stencil printing, flexographic printing, lithography, gravure printing, soft lithography, xerography, imprinting (embossing), micro dispensing, friction transfer printing The radiation curable silicone composition can be applied onto the first inorganic barrier coating using conventional printing methods such as laser transfer printing and thermal transfer printing. The particular method chosen will depend on several factors including the rheology of the silicone composition, the desired thickness of the coating, the application temperature, and the desired resolution. The amount of silicone composition is sufficient to form a cured silicone resin film having a thickness of 0.06 to 30 μm in method step (iii) as described below.

  Where the radiation curable silicone composition includes a solvent, the method may further include removing at least a portion of the solvent from the silicone film. The solvent can be removed by heating the silicone membrane at 30 ° C. to 150 ° C. for 1 minute to 5 minutes, alternatively 60 ° C. to 120 ° C. for 1 minute to 5 minutes.

During step (ii) of the first photolithographic method, in the upper region of the electronic device, the film is exposed to radiation having a wavelength of 150 nm to 800 nm, alternatively 250 nm to 450 nm, so that at least one exposed region and at least A partially exposed membrane with one unexposed area is created. The light source used is typically a medium pressure mercury lamp. The radiation dose is typically from 0.1 mJ / cm ^{2 to} 5,000 mJ / cm ² , alternatively from 250 mJ / cm ^{2 to} 1,300 mJ / cm ² . The film area above the electronic device is exposed to radiation through a photomask.

  During step (iii) of the first photolithographic process, the unexposed areas of the partially exposed film are removed with a developing solvent to form a patterned film. A developing solvent is an organic solvent in which the unexposed areas of the partially exposed film are at least partially soluble and the exposed areas are essentially insoluble. Developer solvents typically have from 3 to 20 carbon atoms. Examples of developing solvents include ketones such as methyl isobutyl ketone and methyl pentyl ketone; ethers such as n-butyl ether and polyethylene glycol monomethyl ether; esters such as ethyl acetate and γ-butyrolactone; aliphatic carbonization such as nonane, decalin and dodecane Hydrogen; and aromatic hydrocarbons such as mesitylene, xylene and toluene. The developing solvent can be applied by any conventional method including spraying, dipping and storage (pooling). Preferably, the developing solvent is applied by creating a pool of solvent on a stationary substrate and then spin drying the substrate. The developing solvent is typically used at a temperature from room temperature to 100 ° C. However, the specific temperature will depend on the chemical properties of the solvent, the boiling point of the solvent, the desired patterning rate, and the required resolution of the photopatterning process.

  Alternatively, if the first interfacial coating is a cured product of a silicone resin having radiation sensitive groups, the first interfacial coating is (i) a radiation curable silicone on the first inorganic barrier coating. Applying the composition to form a film, wherein the silicone composition comprises a silicone resin having an average of at least two silicon-bonded radiation sensitive groups per molecule; (ii) in the upper region of the electronic device; Exposing the film to radiation having a wavelength between 150 nm and 800 nm to create a partially exposed film having at least one exposed area and at least one unexposed area; (iii) the exposed area is substantially Heating the partially exposed film for a predetermined time so that the non-exposed areas are soluble in the developing solvent and the unexposed areas are soluble in the developing solvent; and (Iv) a non-exposed regions of the heated film is removed in the developing solvent, it can be formed by a second photolithography comprising forming a patterned film.

  Step (i) and step (ii) of the second photolithography method are the same as step (i) and step (ii) of the first photolithography method.

  During the second photolithographic step (iii), heating the partially exposed film for a predetermined time such that the exposed area (“exposed area”) is substantially insoluble in the developing solvent. To do. Areas not previously exposed to radiation (“non-exposed areas”) become soluble in the developing solvent. The term “substantially insoluble” means that the exposed areas of the silicone film are not removed to the extent that the surface of the support structure of the substrate is exposed by dissolving in the developing solvent. The term “soluble” means that the unexposed areas of the silicone film are removed by dissolving in a developing solvent, exposing the surface of the substrate support structure. The partially exposed membrane is typically 0.1 minutes to 10 minutes at a temperature of 50 ° C. to 250 ° C., alternatively 1 minute to 5 minutes at a temperature of 100 ° C. to 200 ° C., alternatively Heat at a temperature of 135 ° C. to 165 ° C. for 2 to 4 minutes. The partially exposed film can be heated using conventional equipment such as a hot plate or oven.

  During step (iv) of the second photolithographic method, the unexposed areas of the heated film are removed using a developing solvent to form a patterned film. The unexposed areas of the heated film can be removed as described above in step (iii) of the first photolithography process.

  The second or third photolithography method of forming the first interfacial coating may further comprise heating the patterned film. Typically, the patterned film is heated for a time sufficient to achieve the maximum crosslink density of the silicone without oxidation or degradation. Typically, 1 minute to 300 minutes at a temperature of 50 ° C to 300 ° C, alternatively 10 minutes to 120 minutes at a temperature of 75 ° C to 275 ° C, alternatively 20 minutes at a temperature of 200 ° C to 250 ° C. Heat the patterned film for minutes to 60 minutes.

  According to the method of manufacturing the electronic package, the second inorganic barrier coating is formed on the first interface coating and on any portion of the first inorganic barrier coating not covered by the first interface coating; At least a portion of each electrical contact is not coated. The second inorganic barrier coating and method of forming it are similar to those described and exemplified above for the first inorganic barrier coating.

  The method of manufacturing the electronic package may further include alternately forming at least one interface coating and an inorganic barrier coating on the second inorganic barrier coating. At this time, the alternating interfacial coatings contain a cured product of silicone resin.

Complex of the inorganic barrier and interfacial coatings of the electronic package, low water vapor transmission rate, typically have a ^{1 × 10 -7 g / m 2} / day to 3 g / m ² / day. The coating also has low permeability to oxygen and metal ions such as copper and aluminum. Further, the coating can be transparent or non-transparent to light in the visible region of the electromagnetic spectrum. Furthermore, the coating has high resistance to cracking and low compressive stress.

  The method of manufacturing the electronic package of the present invention can be carried out using conventional equipment and techniques and readily available silicone compositions. For example, the inorganic barrier coating can be deposited using chemical vapor deposition and physical vapor deposition. Moreover, the interfacial coating can be formed using conventional methods of applying and curing the silicone composition. In addition, the method of the present invention can be extended to a high-throughput manufacturing method.

  The electronic package of the present invention is useful for manufacturing a wide range of consumer electronic products including light-emitting arrays or displays, calculators, telephones, televisions, and mainframe and personal computers.

  The following examples are presented to better illustrate the method of forming the interfacial coatings of the present invention, but should not be construed as limiting the invention as set forth in the appended claims. . Unless otherwise indicated, all parts and percentages shown in the examples are on a weight basis. The following methods and materials were used in the examples.

<NMR spectrum>
Nuclear magnetic resonance spectra ( ²⁹ Si NMR and ¹³ C NMR) of the silicone resin were obtained using a Varian Mercury 400 MHz NMR spectrometer. The resin (0.5 g-1.0 g) was dissolved in 2.5 mL-3 mL chloroform-d in a 0.5 oz glass vial. The solution was transferred to a Teflon NMR tube and ₃ mL to 4 mL of a Cr (acac) ₃ chloroform-d (0.04 M) solution was added to the tube.

<Molecular weight>
The weight average molecular weight (M _w ) of the silicone resin having a radiation sensitive group is determined using a 35 ° C. PLgel (Polymer Laboratories, Inc.) 5-μm column, a 1 mL / min THF mobile phase, and a differential refractive index detector. Obtained by gel permeation chromatography (GPC). Polystyrene conversion was used for the calibration curve (tertiary). If the mobile phase was other than toluene, the _Mw of the hydrogensilsesquioxane resin was similarly determined.

<Reagent>
Dow Corning® 9820 Photocatalyst: 1% 3-iodotoluene, 5% 2-isopropylthioxanthone, 41% ((3-methylphenyl) ((C12-13 branched) phenyl) iodonium hexafluoroantimony And a mixture containing 50% 1-decanol.

  Irgacure® 819 Photoinitiator: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (sold by Ciba Specialty Chemicals).

[Example 1]
Toluene (2,400 g), 2.40 mol 3-glycidoxypropyltrimethoxysilane, 4.80 mol methyltrimethoxysilane, 28.8 mol water, 2.4 mL tetramethylammonium hydroxide solution (25% aqueous system) ), And 2,400 g of methanol were mixed in the flask. The mixture was stirred and heated at reflux for 2 hours, during which time 6,950 g of solvent, primary methanol, was removed by distillation using a Dean-Stark trap. During distillation, toluene was added to the mixture to keep the resin concentration constant. The temperature of the mixture was gradually increased to about 110 ° C. in about 1 hour. The mixture was then cooled to room temperature. Acetic acid (3.4 mL) was then added dropwise to the stirred mixture over 1 hour. The mixture was washed with 1,600 mL deionized water (10 times) and then filtered. Toluene was removed using a rotary evaporator at 40 ° C. under reduced pressure. The residue is left at room temperature under vacuum (1 Pa) for 3 hours, the formula determined by ²⁹ Si NMR and ¹³ C NMR:

And a silicone resin having a weight average molecular weight of 1,900.

[Example 2]
Toluene (80 g), 0.20 mol 3-methacryloxypropyltrimethoxysilane, 0.40 mol phenyltrimethoxysilane, 2.40 mol water, 1 g 50% (w / w) aqueous solution of cesium hydroxide, 200 g Methanol and 40 mg of 2,6-di-tert-butyl-4-methylphenol were combined in the flask. The solution was heated at reflux for 1 hour, during which time 250 g of solvent, primary methanol, was removed by distillation using a Dean-Stark trap. Distilled toluene was added to the mixture to keep the resin concentration constant. The temperature of the mixture was gradually increased to about 105 ° C. in about 1 hour. The mixture was then cooled to room temperature. Toluene was removed using a rotary evaporator at 40 ° C. under reduced pressure. The residue is left at room temperature under vacuum (1 Pa) for 3 hours, the formula determined by ²⁹ Si NMR and ¹³ C NMR:

And a silicone resin having a weight average molecular weight of 8,294.

Example 3
A solution of 5% Dow Corning® 9820 Photocatalyst dissolved in the silicone resin of Example 1 was passed through a 0.2 μm filter. A piece of felt (1.5 inch x 0.75 inch x 0.25 inch) was cut from a general purpose ink eraser used as an inking pad. The felt was placed in a petri dish and impregnated with a resin solution. This resin was transferred from the felt pad to the silicon substrate using a positive image rubber stamp. The coating was exposed to about 1 J / cm ² of UV radiation (200 nm to 320 nm) at 450 W / inch using a Fusion UV Light System equipped with a mercury H-type bulb to obtain a tack-free film.

Example 4
A solution of 30% of the silicone resin of Example 2 and 10% of Irgacure® 819 Photoinitiator in propylene glycol methyl ether acetate was passed through a 0.2 μm filter. A piece of felt (1.5 inch x 0.75 inch x 0.25 inch) was cut from a general purpose eraser used as a stamp pad. The felt was placed in a petri dish and impregnated with a resin solution. This resin was transferred from the felt pad to the silicon substrate using a positive image rubber stamp. The coating was exposed to about 1 J / cm ² of UV radiation (200 nm to 320 nm) at 450 W / inch using a Fusion UV Light System equipped with a mercury H-type bulb to obtain a tack-free film.

Claims (12)

An electronic package,
A substrate,
At least one electronic device disposed on or in the substrate and having electrical contacts;
A first inorganic barrier coating on the substrate and the electronic device;
A first interface coating on the first inorganic barrier coating in an upper region of the electronic device, the first interface coating comprising a cured product of a silicone resin;
A second inorganic barrier coating on the first interface coating and on any portion of the first inorganic barrier coating not covered by the first interface coating, wherein at least a portion of each electrical contact is Electronic package without coating.   The electronic package of claim 1, wherein the first inorganic barrier coating is a single layer coating consisting of one layer of inorganic material.   The electronic package of claim 2, wherein the single-layer coating has a thickness of 0.03 μm to 3 μm.   The electronic package of claim 1, wherein the first inorganic barrier coating is a multi-layer coating consisting of two or more layers of at least two different inorganic materials.   The electronic package according to claim 4, wherein the multilayer coating has a thickness of 0.06 μm to 5 μm.   The electronic package of claim 1, wherein the package further comprises at least one interfacial coating and at least one inorganic barrier coating alternately on the second inorganic barrier coating. A method of manufacturing an electronic package comprising:
Forming a first inorganic barrier coating on the substrate and on at least one electronic device disposed on or in the substrate and having electrical contacts;
Forming a first interfacial coating comprising a cured product of a silicone resin on the first inorganic barrier coating in an upper region of the electronic device; and on the first interfacial coating and the first interfacial coating A method of manufacturing an electronic package comprising forming a second inorganic barrier coating on any portion of the first inorganic barrier coating that is not covered by a coating, wherein at least a portion of each electrical contact is not coated .   (I) applying a curable silicone composition comprising a silicone resin on the first inorganic barrier coating in the upper region of the electronic device to form a film; 8. The method of claim 7, formed by a method comprising ii) curing the silicone resin of the membrane.   9. The method of claim 8, wherein the curable silicone composition is selected from a hydrosilylation curable silicone composition, a condensation curable silicone composition, a radiation curable silicone composition, and a peroxide curable silicone composition. .   The method of claim 8, wherein the curable silicone composition is applied onto the first inorganic barrier coating by printing.   The silicone resin has radiation sensitive groups and the first interfacial coating comprises (i) an average of at least two silicon-bonded radiation sensitive groups per molecule on the first inorganic barrier coating. Applying a radiation curable silicone composition comprising a silicone resin having, to form a film; (ii) exposing the film to radiation having a wavelength of 150 nm to 800 nm in the upper region of the electronic device; Creating a partially exposed film having one exposed area and at least one unexposed area; and (iii) removing the unexposed area of the heated film with a developing solvent The method according to claim 7, wherein the method is formed by a photolithography method including forming a film.   The silicone resin has radiation sensitive groups and the first interfacial coating comprises (i) an average of at least two silicon-bonded radiation sensitive groups per molecule on the first inorganic barrier coating. Applying a radiation curable silicone composition comprising a silicone resin having, to form a film; (ii) exposing the film to radiation having a wavelength of 150 nm to 800 nm in the upper region of the electronic device; Creating a partially exposed film having one exposed region and at least one unexposed region; (iii) the exposed region is substantially insoluble in the developing solvent and the unexposed region is in the developing solvent. Heating the partially exposed film for a predetermined time to become soluble, and (iv) developing the unexposed areas of the heated film with a developing solvent The method of claim 7 which is removed, is formed by photolithography comprising forming a patterned film.

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